CN112645423A - Lignin-based polymer flocculant and preparation method thereof - Google Patents
Lignin-based polymer flocculant and preparation method thereof Download PDFInfo
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- lignin
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- enzymatic hydrolysis
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- 229920005610 lignin Polymers 0.000 title claims abstract description 101
- 229920000642 polymer Polymers 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims description 22
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 21
- 230000007071 enzymatic hydrolysis Effects 0.000 claims description 21
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000003999 initiator Substances 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 18
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 14
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 14
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 12
- 230000002209 hydrophobic effect Effects 0.000 claims description 11
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims description 11
- 125000002091 cationic group Chemical group 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 9
- 239000003431 cross linking reagent Substances 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 230000002255 enzymatic effect Effects 0.000 claims description 4
- 238000003828 vacuum filtration Methods 0.000 claims description 4
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 claims description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims 2
- 239000007787 solid Substances 0.000 abstract description 25
- 239000010865 sewage Substances 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 13
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 229920002521 macromolecule Polymers 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 238000004581 coalescence Methods 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 239000000725 suspension Substances 0.000 description 18
- 238000003756 stirring Methods 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000012360 testing method Methods 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 230000001376 precipitating effect Effects 0.000 description 8
- 238000012216 screening Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000002332 oil field water Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000007764 o/w emulsion Substances 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010795 Steam Flooding Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Medicinal Chemistry (AREA)
- Analytical Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses a lignin-based polymer flocculant and a preparation method thereof. According to the invention, polyacrylamide long-chain branched molecules are grafted on enzymolysis lignin macromolecules, so that the contact area of the enzymolysis lignin macromolecules on an oil-water interface is increased, and various functional structural units are introduced into the molecules, so that the interface activity and the adsorption capacity of the enzymolysis lignin macromolecules are increased, an oil-water interface film can be damaged more quickly, and coalescence oil drops and solid suspended particles in water can be better adsorbed. The prepared lignin-based polymer flocculant is used alone or is compounded with a reverse demulsifier, so that emulsified oil and solid suspended particles in oily sewage of an oil field can be quickly and effectively removed, and a technical support is provided for stable operation, safety and environmental protection of a technical water treatment system of the oil field.
Description
Technical Field
The invention relates to the technical field of oil field oily sewage treatment agents and crude oil gathering and transportation oil-water separation treatment, in particular to a lignin-based polymer flocculant and a preparation method thereof.
Background
At present, most of domestic oil fields are in a development stage with high extraction degree and ultrahigh water content, the common use of injected water for displacement of reservoir oil and the wide application of enhanced oil recovery technologies such as chemical flooding, steam flooding and the like are adopted, and yield increasing measures such as acidification, fracturing, profile control, water shutoff and the like are implemented, so that the specific gravity of oil-in-water (O/W) emulsion in oil field extraction liquid is increased more and more, the emulsification degree of the O/W emulsion is more serious, the emulsion is more complex, and the treatment difficulty is higher. With the further development of oil fields, the problems of demulsification of O/W emulsion in oil field produced fluid and oil removal of oily sewage are more prominent.
At present, the water treatment agents used for oil-in-water emulsion breaking at home and abroad can be roughly divided into a plurality of classes, such as low molecular electrolytes, alcohols, surfactants, polymers, and the like.
The research on oil field sewage treatment agents at home and abroad has a history of over ten years, but with the common use of oil field production increasing measures and the continuous improvement of environmental protection reinjection requirements, the current oil field water treatment technology cannot completely meet the requirements of oil field water treatment, and novel efficient water treatment agents are continuously researched and developed to solve the problems encountered in the current oil field water treatment.
Lignin, as a high-reserve natural renewable resource, is not currently utilized effectively and reasonably. Less than 2% of the total industrial lignin produced around 1.5-1.8 million tons worldwide per year is utilized. With the revolution of green energy, bioethanol appears on a large scale, particularly, the 2 nd generation cellulosic ethanol takes crop straws as raw materials, and the generated byproduct enzymatic hydrolysis lignin is a new raw material source of industrial lignin at present.
The extraction and separation reaction process of the enzymatic hydrolysis lignin is mild, ash and sugar in the obtained enzymatic hydrolysis lignin are low, and a large amount of active functional group structures such as phenolic hydroxyl, alcoholic hydroxyl and the like are still reserved in the molecular structure of the enzymatic hydrolysis lignin. However, the lack of strongly hydrophilic functional groups in the molecule and the occupation of reactive, highly reactive sites by other functional groups limit the water solubility and chemical reactivity. Lignin generally contains active groups such as aromatic groups, phenolic hydroxyl groups, alcoholic hydroxyl groups, carbonyl groups, methoxy groups, carboxyl groups, double bonds and the like, so that a series of chemical modifications can be carried out. After lignin is modified, new or more functional groups can be obtained, and the modified lignin becomes a derivative product with unique properties and wider application value.
Lignin is an organic high molecular polymer which has a complex three-dimensional network and forms a large number of active groups, and has natural advantages when used as a flocculating agent, i.e. the lignin can adsorb colloidal particles in water through electrostatic attraction or hydrogen bond; secondly, colloidal particles and suspended matters can be caught and swept by a spatial reticular macromolecular structure to generate sedimentation.
Although lignin can be directly used as a flocculant, the average relative molecular mass is low, and the active adsorption points are few, which directly influence the flocculation performance of the lignin. Therefore, various methods are proposed to modify lignin to change the spatial configuration of lignin, increase the relative molecular mass, introduce a functional group with flocculation property, and further improve the flocculation property of lignin.
The study of the lignin-based water treatment agent started in the 60's of the 20 th century, but it has rapidly progressed in the last 10 years. The improvement of the application performance of the lignin water treatment agent by the methods of modification and graft copolymerization is a main direction of research. However, most of researches are directed to the field of industrial wastewater treatment with high metal ion content and high decolorization requirement, and relatively few researches are specially directed to oil-containing sewage treatment of oil-in-water emulsion type with high solid suspension and complex emulsification in oil fields.
In conclusion, the treatment capacity of the oil-containing sewage of the oil field is increased year by year, the treatment difficulty is increased day by day, and the environment-friendly reinjection requirement is severe day by day, generally adopted water treatment agents are mostly low-molecular electrolyte or chemical synthesis agents, the increasingly complex situation and severe requirement of the oil field water treatment can not be met gradually, and new problems are caused because the treated water needs to be reinjected, so that the underground water is easily polluted and new problems are generated. Therefore, the lignin-based oily sewage biological flocculant is developed, on one hand, the requirement of oil field oily sewage treatment is met, on the other hand, the reasonable utilization of lignin resources and the safety and environmental protection of reinjection water are realized, and the lignin-based oily sewage biological flocculant has important significance on the safety, environmental protection and sustainable development of oil field production.
Disclosure of Invention
The invention aims to provide a lignin-based polymer flocculant for oily sewage. Functional structural units are introduced into the macromolecular chains of the enzymatic hydrolysis lignin, so that the interaction between the lignin material and emulsified oil drops and solid suspended matters in the oily sewage of the oil field is improved, the adsorption and coiling and sweeping combination performance of the material is improved, the performance of treating the oily sewage of the oil field is improved, and the effect that the treated water quality meets the requirements of oil field production and reinjection for environmental protection is achieved.
The invention provides a lignin-based polymer flocculant, which is characterized by comprising enzymatic hydrolysis lignin grafted with functional structural units, wherein the functional structural units comprise polyacrylamide shown in a formula I, a cation structural unit shown in a formula II and a hydrophobic structural unit shown in the formula:
wherein R is3、R4、R5、R6、R7、R8、R10Each independently selected from H or C1-C4 alkyl; x is halogen, preferably Cl or Br.
According to some embodiments of the invention, the source of the cationic building blocks is selected from one or more of methacryloyloxyethyltrimethyl ammonium chloride, acryloyloxyethyltrimethyl ammonium chloride, dimethyldiallylammonium chloride and diallyldimethylammonium chloride.
According to some embodiments of the invention, the source of the cationic building blocks is methacryloyloxyethyltrimethylammonium chloride.
According to some embodiments of the invention, the source of the hydrophobic building blocks is selected from one or more of butyl acrylate, methyl methacrylate and styrene.
According to some embodiments of the invention, the source of the hydrophobic building blocks is butyl acrylate.
A second aspect of the present invention is to provide a method for preparing a lignin-based polymeric flocculant, comprising the steps of;
s1, carrying out a first reaction on the enzymatic hydrolysis lignin and an acrylamide monomer under the action of an initiator;
s2, adding a polymeric dispersant, mixing, adding a cationic monomer and a hydrophobic monomer, adding a cross-linking agent, and carrying out a second reaction;
s3, purifying the product of the second reaction to obtain the lignin-based polymer flocculant.
According to some embodiments of the invention, the purification comprises soaking the precipitate, washing with water, drying, crushing and sieving steps.
According to some embodiments of the invention, further comprising a step of purifying the enzymatically hydrolyzed lignin.
According to some embodiments of the invention, the step of purifying enzymatically hydrolyzed lignin comprises:
s11, adding the enzymatic hydrolysis lignin into water, adjusting the pH value of the solution to 12.0-13.0, treating for a period of time, and performing vacuum filtration to obtain a first filter cake;
s12, adding the first filter cake into water, adjusting the pH value of the solution to 2.0-3.0, treating for a period of time, and then carrying out vacuum filtration to obtain a second filter cake;
and S13, adding the second filter cake into a dilute hydrochloric acid aqueous solution, treating for a period of time, filtering, washing with water and drying to obtain the purified enzymatic hydrolysis lignin.
According to some embodiments of the invention, the initiator is selected from one or more of potassium persulfate, sodium bisulfite, and 2, 2-azobisisobutylamidine dihydrochloride.
According to some embodiments of the invention, the initiator comprises potassium persulfate and sodium bisulfite.
According to some embodiments of the invention, the polymeric dispersant is selected from one or more of polyvinyl alcohol, stearyl polyoxyethylene ether, and OP-10.
According to some embodiments of the invention, the polymeric dispersant is polyvinyl alcohol.
According to some embodiments of the invention, the cross-linking agent is selected from one or more of N, N' -methylenebisacrylamide, polyethyleneimine and polyethylene glycol.
According to some embodiments of the invention, the cross-linking agent is N, N' -methylenebisacrylamide.
According to some embodiments of the present invention, in the enzymatic hydrolysis lignin, the acrylamide, the cationic monomer and the hydrophobic monomer, the acrylamide accounts for 20% to 40%, the cationic monomer accounts for 5% to 20%, the hydrophobic monomer accounts for 5% to 10%, and the balance is the enzymatic hydrolysis lignin.
According to some embodiments of the invention, the cross-linking agent is 0.1% to 5% of the total amount of the enzymatic hydrolysis lignin, acrylamide and all functional monomers, by weight.
According to some embodiments of the invention, the cross-linking agent is 0.5% to 1% of the total amount of the enzymatic hydrolysis lignin, acrylamide and all functional monomers, by weight.
According to some embodiments of the invention, the initiator is 0.2% to 1.0% of the total amount of the enzymatic hydrolyzed lignin, acrylamide, and all functional monomers, by weight.
According to some embodiments of the invention, the initiator is 0.45% to 0.8% of the total amount of the enzymatic hydrolyzed lignin, acrylamide, and all functional monomers, by weight.
According to some embodiments of the invention, the ratio of potassium persulfate to sodium bisulfite in the initiator is from 1: (1-10).
According to some embodiments of the invention, the ratio of potassium persulfate to sodium bisulfite in the initiator is from 1: (3-8).
According to some embodiments of the invention, the polymeric dispersant is present in an amount ranging from 3% to 8% by weight of the total amount of the product of the first reaction synthesis.
The total amount of the product synthesized in the first reaction, namely the total amount of the solution obtained after the first step reaction, comprises the total mass of lignin, water and acrylamide.
The invention has the beneficial effects that:
the invention relates to a lignin-based polymer flocculant and a preparation method thereof, wherein polyacrylamide long-chain branched molecules are grafted on enzymolysis lignin macromolecules, so that the contact area of the enzymolysis lignin macromolecules on an oil-water interface is increased, and various functional structural units are introduced into the molecules, so that the interface activity and the adsorption capacity of the enzymolysis lignin macromolecule flocculant are increased, an oil-water interface film can be damaged more quickly, and coalescence oil drops and solid suspended particles in water can be better adsorbed. The prepared lignin-based polymer flocculant is used alone or is compounded with a reverse demulsifier, so that emulsified oil and solid suspended particles in oily sewage of an oil field can be quickly and effectively removed, and a technical support is provided for stable operation, safety and environmental protection of a technical water treatment system of the oil field.
Detailed Description
The present invention will be described in detail with reference to examples. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation. It is also to be understood that the reference to method steps and data associated therewith in this embodiment does not exclude the interposition of other combinations of method steps and proportions of data, and the endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and such ranges or values are to be understood as encompassing values close to these ranges or values and are to be considered as the scope of the practice of the invention.
The oil removal rate and the solid suspension removal rate are tested by adopting a tube test method according to oil industry standards SY/T0530-93 and SY/T5797-93. Pouring crude oil sewage into a test tube with a plug scale, putting the test tube into a constant-temperature water bath for preheating, adding a certain amount of lignin-based flocculant, manually shaking for 200 times, fully mixing uniformly, placing the test tube into the constant-temperature water bath for standing for 30min, and observing and recording the conditions of a water phase, an oil phase and an interface. And an ultraviolet spectrophotometer and a filtering experimental device are used according to the standard to measure the oil content and the solid suspended matter content in the treated water, so as to calculate the oil removal rate and the solid suspended matter removal rate of the lignin-based flocculant.
And (3) enzymolysis of lignin:
the manufacturer: shandong Longli biological science and technology, batch number: 2018060704,
appearance: brown small pieces and powder
The content of lignin: 94.8 percent
Residual sugar content: 0.12 percent of
Ash content: 0.57 percent
Moisture content: 16.5 percent
Content of phenolic hydroxyl group: 12.9 percent
The detection is according to the standard Q/1482CLL 017-2015.
The molecular weight of the polyvinyl alcohol of the polymeric dispersant is 2-3 ten thousand.
And (3) purifying enzymolysis lignin:
100g of enzymatically hydrolyzed lignin was weighed into 1000mL of distilled water, the pH of the solution was adjusted to 12.5. + -. 0.1 with aqueous sodium hydroxide solution (20 wt.%), and the solution was mechanically stirred for 30 min. Filtering under reduced pressure, adjusting pH of the filtrate to 2.0-3.0 with 10 wt.% dilute hydrochloric acid aqueous solution, filtering under reduced pressure to obtain filter cake, pouring the filter cake into 10 wt.% dilute hydrochloric acid aqueous solution, mechanically stirring for 30min, filtering, washing with water, and vacuum drying at 40 deg.C to constant weight.
Example 1
1. Weighing 24.0g of purified lignin, adding into a three-necked bottle, adding 60.0g of deionized water, introducing nitrogen, and stirring for 30 min. A complex initiator of 0.02g of potassium persulfate and 0.16g of sodium bisulfite and 8.0g of an acrylamide monomer were added thereto, and the mixture was reacted at 60 to 80 ℃ for 2 hours.
2. Adding 5.0g of polyvinyl alcohol, stirring for 30min, adding 4.0g of methacryloyloxyethyl trimethyl ammonium chloride and 4.0g of butyl acrylate, adding 0.03g of N, N' -methylene bisacrylamide after 20min, and continuously reacting for 4 hours.
3. And after the reaction is finished, soaking and precipitating the product by using ethanol, and then washing, drying, crushing and screening the product to obtain the lignin-based polymer flocculant.
The test shows that the lignin-based polymer flocculant has the oil removal rate of 89.8 percent and the solid suspension removal rate of 72.1 percent, which shows that the lignin-based polymer flocculant has better oil removal and solid suspension removal effects.
Example 2
1. Weighing 24.0g of purified lignin, adding into a three-necked bottle, adding 60.0g of deionized water, introducing nitrogen, and stirring for 30 min. A complex initiator of 0.08g of potassium persulfate and 0.24g of sodium hydrogen sulfite and 12.0g of an acrylamide monomer were added thereto, and the mixture was reacted at 60 to 80 ℃ for 2 hours.
2. Adding 5.0g of polyvinyl alcohol, stirring for 30min, adding 2.0g of methacryloyloxyethyl trimethyl ammonium chloride and 2.0g of butyl acrylate, adding 0.03g of N, N' -methylene bisacrylamide after 20min, and continuously reacting for 4 hours.
3. And after the reaction is finished, soaking and precipitating the product by using ethanol, and then washing, drying, crushing and screening the product to obtain the lignin-based polymer flocculant.
The test shows that the lignin-based polymer flocculant has the oil removal rate of 88.7 percent and the solid suspension removal rate of 63.2 percent, which shows that the lignin-based polymer flocculant has better oil removal and solid suspension removal effects.
Example 3
1. Weighing 16.0g of purified lignin, adding into a three-necked bottle, adding 60.0g of deionized water, introducing nitrogen, and stirring for 30 min. A complex initiator of 0.02g of potassium persulfate and 0.16g of sodium hydrogen sulfite and 16.0g of acrylamide monomer were added thereto, and the mixture was reacted at 60 to 80 ℃ for 2 hours.
2. Adding 5.0g of polyvinyl alcohol, stirring for 30min, adding 4.0g of methacryloyloxyethyl trimethyl ammonium chloride and 4.0g of butyl acrylate, adding 0.03g of N, N' -methylene bisacrylamide after 20min, and continuously reacting for 4 hours.
3. And after the reaction is finished, soaking and precipitating the product by using ethanol, and then washing, drying, crushing and screening the product to obtain the lignin-based polymer flocculant.
The test shows that the lignin-based polymer flocculant has the oil removal rate of 93.7 percent and the solid suspension removal rate of 69.5 percent, which shows that the lignin-based polymer flocculant has better oil removal and solid suspension removal effects.
Example 4
1. Weighing 24.0g of purified lignin, adding into a three-necked bottle, adding 60.0g of deionized water, introducing nitrogen, and stirring for 30 min. A complex initiator of 0.08g of potassium persulfate and 0.24g of sodium hydrogen sulfite and 8.0g of an acrylamide monomer were added thereto, and the mixture was reacted at 60 to 80 ℃ for 1 hour.
2. Adding 5.0g of polyvinyl alcohol, stirring for 30min, adding 4.0g of methacryloyloxyethyl trimethyl ammonium chloride and 4.0g of butyl acrylate, adding 0.03g of N, N' -methylene bisacrylamide after 20min, and continuously reacting for 6 hours.
3. And after the reaction is finished, soaking and precipitating the product by using ethanol, and then washing, drying, crushing and screening the product to obtain the lignin-based polymer flocculant.
The test shows that the lignin-based polymer flocculant has oil removal rate of 92.8% and solid suspension removal rate of 71.6%, which indicates that the lignin-based polymer flocculant has better oil removal and solid suspension removal effects.
Example 5
1. Weighing 24.0g of purified lignin, adding into a three-necked bottle, adding 60.0g of deionized water, introducing nitrogen, and stirring for 30 min. A complex initiator of 0.08g of potassium persulfate and 0.24g of sodium hydrogen sulfite and 8.0g of an acrylamide monomer were added thereto, and the mixture was reacted at 60 to 80 ℃ for 1 hour.
2. Adding 5.0g of polyvinyl alcohol, stirring for 30min, adding 4.0g of dimethyldiallylammonium chloride and 4.0g of butyl acrylate, adding 0.03g of N, N' -methylenebisacrylamide after 20min, and continuously reacting for 6 h.
3. And after the reaction is finished, soaking and precipitating the product by using ethanol, and then washing, drying, crushing and screening the product to obtain the lignin-based polymer flocculant.
The test shows that the lignin-based polymer flocculant has oil removal rate of 89.2 percent and solid suspension removal rate of 63.5 percent, and has relatively low oil removal and solid suspension removal effects.
Example 6
1. Weighing 24.0g of purified lignin, adding into a three-necked bottle, adding 60.0g of deionized water, introducing nitrogen, and stirring for 30 min. A complex initiator of 0.08g of potassium persulfate and 0.24g of sodium hydrogen sulfite and 8.0g of an acrylamide monomer were added thereto, and the mixture was reacted at 60 to 80 ℃ for 1 hour.
2. Adding 5.0g of polyvinyl alcohol, stirring for 30min, adding 4.0g of methacryloyloxyethyl trimethyl ammonium chloride and 4.0g of methyl methacrylate, adding 0.03g of N, N' -methylene bisacrylamide after 20min, and continuously reacting for 6 hours.
3. And after the reaction is finished, soaking and precipitating the product by using ethanol, and then washing, drying, crushing and screening the product to obtain the lignin-based polymer flocculant.
The test shows that the lignin-based polymer flocculant has the oil removal rate of 88.3 percent and the solid suspension removal rate of 62.1 percent, and has relatively low oil removal and solid suspension removal effects.
Example 7
1. Weighing 24.0g of purified lignin, adding into a three-necked bottle, adding 60.0g of deionized water, introducing nitrogen, and stirring for 30 min. 0.18g of potassium persulfate and 8.0g of an acrylamide monomer were added thereto, and the mixture was reacted at 60 to 80 ℃ for 1 hour.
2. Adding 5.0g of polyvinyl alcohol, stirring for 30min, adding 4.0g of methacryloyloxyethyl trimethyl ammonium chloride and 4.0g of methyl methacrylate, adding 0.03g of N, N' -methylene bisacrylamide after 20min, and continuously reacting for 6 hours.
3. And after the reaction is finished, soaking and precipitating the product by using ethanol, and then washing, drying, crushing and screening the product to obtain the lignin-based polymer flocculant.
The oil removal rate of the lignin-based polymer flocculant synthesized by tests is 65.2%, the solid suspension removal rate is 34.1%, and the results show that the effect of a single initiator is poor, and the oil removal and solid suspension removal effects are relatively low.
Example 8
1. Weighing 24.0g of purified lignin, adding into a three-necked bottle, adding 60.0g of deionized water, introducing nitrogen, and stirring for 30 min. 0.18g of sodium hydrogen sulfite and 8.0g of acrylamide monomer were added thereto, and the mixture was reacted at 60 to 80 ℃ for 1 hour.
2. Adding 5.0g of polyvinyl alcohol, stirring for 30min, adding 4.0g of methacryloyloxyethyl trimethyl ammonium chloride and 4.0g of methyl acrylate, adding 0.03g of N, N' -methylene bisacrylamide after 20min, and continuously reacting for 6 hours.
3. And after the reaction is finished, soaking and precipitating the product by using ethanol, and then washing, drying, crushing and screening the product to obtain the lignin-based polymer flocculant.
The oil removal rate of the lignin-based polymer flocculant synthesized by tests is 68.4%, and the solid suspension removal rate is 38.4%, which shows that the effect of a single initiator is poor, and the oil removal and solid suspension removal effects are relatively low.
While the embodiments of the present invention have been described in detail, it should be understood that the invention is not limited thereto, and that various simple modifications, including combinations of various materials of the same type and related parameters in any other suitable manner, can be made by those skilled in the art without departing from the present invention, and that such simple modifications and combinations should be considered as the present invention disclosed, and all fall within the scope of the present invention.
Claims (10)
1. The lignin-based polymer flocculant is characterized by comprising enzymatic hydrolysis lignin grafted with functional structural units, wherein the functional structural units comprise polyacrylamide shown as a formula I, a cationic structural unit shown as a formula II and a hydrophobic structural unit shown as a formula:
wherein R is3、R4、R5、R6、R7、R8、R10Each independently selected from H or C1-C4 alkyl; x is halogen, preferably Cl or Br.
2. The flocculant according to claim 1, wherein the cationic structural units are derived from one or more selected from the group consisting of methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, dimethyldiallylammonium chloride and diallyldimethylammonium chloride, preferably methacryloyloxyethyl trimethyl ammonium chloride.
3. Flocculant according to claim 1 or 2, characterized in that the source of the hydrophobic building blocks is selected from one or more of butyl acrylate, methyl methacrylate and styrene, preferably butyl acrylate.
4. A method of preparing a lignin-based polymeric flocculant, comprising the steps of:
s1, carrying out a first reaction on the enzymatic hydrolysis lignin and an acrylamide monomer under the action of an initiator;
s2, adding a polymeric dispersant, mixing, adding a cationic monomer and a hydrophobic monomer, adding a cross-linking agent, and carrying out a second reaction;
s3, purifying the product of the second reaction to obtain a lignin-based polymer flocculant;
preferably, the purification comprises the steps of soaking the precipitate, washing with water, drying, crushing and sieving.
5. The method according to claim 4, further comprising a step of purifying the enzymatic lignin;
preferably, the step of purifying the enzymatic hydrolysis lignin comprises:
s11, adding the enzymatic hydrolysis lignin into water, adjusting the pH value of the solution to 12.0-13.0, treating for a period of time, and performing vacuum filtration to obtain a first filter cake;
s12, adding the first filter cake into water, adjusting the pH value of the solution to 2.0-3.0, treating for a period of time, and then carrying out vacuum filtration to obtain a second filter cake;
and S13, adding the second filter cake into a dilute hydrochloric acid aqueous solution, treating for a period of time, filtering, washing with water and drying to obtain the purified enzymatic hydrolysis lignin.
6. The process of claim 4 or 5, wherein the initiator is selected from one or more of potassium persulfate, sodium bisulfite and 2, 2-azobisisobutylamidine dihydrochloride; preferably including potassium persulfate and sodium bisulfite;
and/or the polymeric dispersant is selected from one or more of polyvinyl alcohol, octadecyl alcohol polyoxyethylene ether and OP-10, and is preferably polyvinyl alcohol;
and/or the cross-linking agent is selected from one or more of N, N '-methylene bisacrylamide, polyethyleneimine and polyethylene glycol, and is preferably N, N' -methylene bisacrylamide.
7. The method according to any one of claims 4 to 6, wherein the enzymatic hydrolysis lignin, the acrylamide, the cationic monomer and the hydrophobic monomer comprise, by weight, 20% to 40% of the acrylamide, 5% to 20% of the cationic monomer, 5% to 10% of the hydrophobic monomer, and the balance of the enzymatic hydrolysis lignin.
8. The method according to any one of claims 4 to 7, wherein the cross-linking agent is present in an amount of 0.1% to 5%, preferably 0.5% to 1%, by weight of the total amount of the enzymatic lignin, acrylamide and all functional monomers.
9. The method according to any one of claims 4 to 8, wherein the initiator is 0.2 to 1.0%, preferably 0.45 to 0.8% by weight of the total amount of the enzymatic hydrolysis lignin, acrylamide and all functional monomers;
and/or the ratio of potassium persulfate to sodium bisulfite in the initiator is 1: (1-10), preferably 1: (3-8).
10. The method of any one of claims 4 to 9, wherein the polymeric dispersant is present in an amount of 3% to 8% by weight of the total amount of the first reaction synthesis product.
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